Washing, bleaching and cleansing agents containing copolymeric n-alkylcarboxylic acid alkyleneimines

ABSTRACT

A washing, bleaching and cleansing agent having a content of from 50 to 99.9 percent, by weight, of customary components of washing, bleaching and cleansing agents and from 0.1 to 50 percent, by weight, of salts of at least one copolymeric Nalkylcarboxylic acid-alkyleneimine, said copolymeric Nalkylcarboxylic acid-alkyleneimine having an average molecular weight of from 500 to 500,000 and the recurring N-alkylcarboxylic acid-alkyleneimine units are of different structure of the formulas I and II where R represents a member selected from the group consisting of H and CH3, R&#39;&#39; represents a member selected from the group consisting of H and CH3, X represents a member selected from the group consisting of H and -CH2- COOH, Y represents a member selected from the group consisting of H, -CH2-COOH and -CH2CH2COOH and n represents an integer of from one to two, the ratio of recurring N-alkylcarboxylic acid-alkyleneimine units of formula I to those of formula II being from one to 100 to 100 to one.

E] r: te States Werdehausen et a].

i atent 91 11 3,718,597 51 *Feb. 27, 1973 WASHING, BLEACHING ANDCLEANSING AGENTS CONTAINING COPOLYMERIC N- ALKYLCARBOXYLIC ACIDALKYLENEIMINES [75] Inventors: Achim Werdehausen; Ullrich Jahnke, bothof Monheim; Gunter Jakobi, Hilden: Guntram Walther, Dusseldorf-Eller,all of Germany [73] Assignee: Henkel & Cie GmbH, Dusseldorf,

Germany [*1 Notice: The portion of the term of this patent subsequent toMarch 21, 1989, has been disclaimed.

[22] Filed: Dec. 1, 1970 [2]] Appl. No.: 94,213

[30] Foreign Application Priority Data Primary Examiner-Mayer WeinblattAttorney-Hammond & Littell [57] ABSTRACT A washing, bleaching andcleansing agent having a content of from 50 to 99.9 percent, by weight,of customary components of washing, bleaching and cleansing agents andfrom 0.1 to 50 percent, by weight, of salts of at least one copolymericN-alkylcarboxylic acid-alkyleneimine, said copolymeric N-alkylcarboxylicacid-alkyleneirnine having an average molecular weight of from 500 to500,000 and the recurring N-alkylcarboxylic acid-alkyleneimine units areof different structure of the formulas I and ll where R represents amember selected from the group consisting of H and CH R represents amember selected from the group consisting of H and CH X represents amember selected from the group consisting of H and -Cl-I -COO H, Yrepresents a member selected from the group consisting of H, CH COOH and-CH -CH COOH and n represents an integer of from one to two, the ratioof recurring N-alkylcarboxylic acid-alkyleneimine units of formula I tothose of formula 11 being from one to 100 to 100 to one.

6 Claims, N0 Drawings WASHING, BLEACHING AND CLEANSING AGENTS CONTAININGCOPOLYMERIC N- ALKYLCARBOXYLIC ACID ALKYLENEIMINES THE PRIOR ART It hasbeen common in the prior art to add to washing and cleansing agents,particularly those which contain bleaching compounds having activeoxygen, complexing aminopolycarboxylie acids or their alkali salts, suchas nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA),or diethylenetriamine pentaacetic acid (DTPA), in order to increase thestability of the bleaching agent, or to protect the optical brightenerscontained in the detergents against an attack by the oxidizing agents.These compounds have, however, certain disadvantages. NTA can protectthe optical brighteners only insufficiently from an oxidizing attack,while EDTA and DTPA are not completely stable against oxidizing agentsand are oxidized to inactive compounds. The compounds named indeedincrease the cleaning properties of washing agents. They are, however,in this respect inferior to the known inorganic builders, particularlyto the polymeric phosphates.

OBJECTS OF THE INVENTION An object of the present invention is theobtaining of washing, bleaching and cleansing agents which haveincorporated therein complexing compounds which have an increasedstability against oxidizing agents, give an increased cleaning propertyto the washing agents and stabilize the optical brighteners present.

Another object of the invention is the obtaining of a washing, bleachingand cleansing agent having a con- I CH-COOH wherein R represents amember selected from the group consisting of H and CH R represents amember selected from the group consisting of H and CH X represents amember selected from the group consisting of H and -CH,-COOH, Yrepresents a member selected from the group consisting of H, CH,-COOHand -CH,-CH,-COOH and n represents an integer of from one to two, theratio of recurring N-alkyl-carboxylic acid-alkyleneimine units offormula I to those of formula 11 being from 1:100 to 100:1.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

DESCRIPTION OF THE INVENTION It has now been discovered that complexingsalts of copolymeric N-alkylcarboxylic acid-alkyleneimines having anaverage molecular weight of from 500 to 500,000, are complexingcompounds for washing, bleaching and cleansing agents which,incorporated in said agents, are distinguished by a good stabilityagainst oxidizing substances, by an improved cleaning property, and byan effective stabilizing of the optical brighteners.

The invention, therefore, comprises a washing, bleaching and cleansingagent having a content of from 50 to 99.9 percent by weight, ofcustomary components of washing, bleaching and cleansing agents and from0.1 to 50 percent, by weight, of salts of at least one copolymericN-alkyl-carboxylic acid-alkyleneimine having an average molecular weightof from 500 to 500,000 and the recurring N-alkyl-carboxylicacid-alkyleneimine units are of different structure of the formula I andII wherein R represents a member selected from the group consisting of Hand CH R represents a member selected from the group consisting of H andCH,, X represents a member selected from the group consisting of H and-CH COOH, Y represents a member selected from the group consisting of H,-CH -COOH and -CH -CH -COOH and n represents an integer of from one totwo, the ratio of recurring N-alkyl-carboxylic acid-alkyleneimine unitsof formula I to those of formula 11 being from one to to 100 to one.

The copolymers are derived from derivatives of ethyleneimine (R=R'=H),propyleneimine (R=R'= CH or from their mixtures (R and R are notidentical). Preferably the copolymers are derived from derivatives ofethyleneimine. The copolymers concerned with, according to theinvention, can have the following composition:

1'. Copolymers of N-succinic acid-ethyleneimine (R=H, X=H) with:

a. N-acetic acid-ethyleneimine (R=H, Y=H, n=l) b. N-propionicacid-ethyleneimine (R=H, Y=H,

c. N-methylenesuccinic acid-ethyleneimine (R=H,

d. N-methyleneglutaric acid-ethyleneimine (R=H,

CH -CH,-COOH, n=2).

2. Copolymers of N-tricarballylic acid-ethyleneimine (R=H, X= CH,-COOH)with:

(a) N-acetic acid-ethyleneimine (R=H, Y=H, n=1) (b) N-propionicacid-ethyleneimine (R=H, Y-H,

(c) N-methylenesuccinic acid-ethyleneimine (R=H,

Y= CH -C0OH, n=2) (d) N-methyleneglutaric acid-ethyleneimine (R=H,

Y= -CH,-CH,-COOH, n=2) (e) N-su'ccinic acid-ethyleneimine (R=H, Y=

CH,-COOH, n=1). The polymeric (N-alkylcarboxylic acid)- ethyleneiminesare amphoteric substances. They can, therefore, depending upon thealkalinity or acidity of the washing, bleaching, and cleansing agents,be present as salts of alkali metals and ammonium salts,

especially salts of sodium and potassium, and as salts of organicammonium bases, as inner salts, or as salts of strong acids, forexample, mineral acids, such as sulfuric acid and organic acids, such asp-toluenesulfonic acid.

The preparation of the polymeric (N-alkylcarboxylic acid)-alkyleneiminescan be done according to various known methods. For the synthesis oflinear polymers, first monomeric ethyleneimine (aziridine) orpropyleneimine is alkylated on the nitrogen atom according to theprinciples of the Michael-Addition, with derivatives ofolefinic-unsaturated carboxylic acids, such as esters, amides andnitriles. Instead of olefinicunsaturated carboxylic derivatives, alsoderivatives of halogenated carboxylic acids can be used for thealkylation on the nitrogen atom. Examples of suitable carboxylic acidderivatives and their reaction products with monomeric alkyleneiminesare summarized in the following Table I.

TABLEI Carboxylic Acid Derivatives Suitable for Reaction AlkyleneimineDerivatives N-acetic acid derivative N-B-propionic acid deriva tiveN-methylenesuccinic acid derivative N-methyleneglutaric acid derivativeN-succinic acid derivative dinitrile of maleic, fumaric, or monobromosuccinic acid f. Triester of cisor N-tricarballylic acid trans-aconiticacid derivative Before the copolymerization one of the derivatives namedunder (a) to (d) is mixed with the derivative named under (e), or one ofthe derivatives named under (a) to (e) is mixed with the derivativenamed under (f), where the molar ratio may be 1:100 to 100:1, preferably1:10 to :1. The copolymerization which may be carried out in thepresence or absence of inert solvents, is catalyzed by Lewis-type acids,for example, neutral sulfuric acid esters, preferably di-lower alkylsulfates, such as dimethyl sulfate, diethyl sulfate, dipropyl sulfate,and dibutyl sulfate, or sulfonic acid esters, preferably lower alkanolesters of alkylsulfonic acids and arylsulfonic acids, such as themethyl, ethyl, propyl and butyl esters of methanesulfonic acid,benzenesulfonic acid, and p-toluenesulfonic acid. The polymerization canalso be conducted in the presence of solvents, especially of the lowerhalogenated hydrocarbons. The polymerization time is usually 2 to 60hours. The reaction temperature is appropriately held between 30 and 90C by cooling. The ester, amide or nitrile derivatives of the copolymeric(N-alkyl carboxylic acid)-alkyleneimines obtained are saponified in aknown manner, for example, by heating with an alkali metal hydroxidesolution such as aqueous sodium or potassium hydroxide. The alkali metalsalts formed can be converted into the free acids by treating withion-exchange resins. By subsequent neutralization with ammonia ororganic ammonium bases, such as mono-, dior triethanolamine, morpholine,or N- methylmorpholine, the free acids can be converted to thecorresponding organic ammonium salts, or by neutralization with strongacids, the free acids can be converted to the corresponding acid salts.

The average molecular weights of the copolymeric (N-alkylcarboxylicacid)-alkyleneimines obtained in this way can vary within wide limitsdepending upon the type and amount of the polymerization catalyst used,the polymerization temperature, and the reaction time. In general, theaverage molecular weight of such linear polymers is between 500 and10,000. By separating out the low molecular components often present inthe mixture, for example, by gel-chromatography on polymerized dextranes(Sephadex"), polymers with varied average molecular weight can beobtained. Since the low molecular components do not disturb, they canremain in the product.

If the N-alkylcarboxylic acid-alkyleneimines used in thecopolymerization still contain unsubstituted ethyleneimine orpropyleneimine, during the polymerization, copolymers are obtained whichare more or less branched depending on the amount of the unsubstitutedalkyleneimines present. The amount of the unsubstituted alkyleneiminesin the starting material should not surpass 50 mol percent andpreferably should be less than 30 mol percent.

A further method of preparation of the salts of the copolymeric(N-alkylcarboxylic acid)-alkyleneimines starts from preformedpolyalkyleneimines having an average molecular weight of from 300 to150,000. The polyalkyleneimines are then reacted in alkaline aqueousmedium with the derivatives or salts, preferably the alkali metal salts,of the above-indicated unsaturated carboxylic acids, or halogenatedcarboxylic acids. The carboxylic acids or their derivatives can bereacted simultaneously or successively with the polyalkyleneimine. Inthe reaction, the amount of the carboxylic acids or their derivatives orsalts should be selected in order that least 50 percent and preferablymore than percent of the primary and secondary amino groups in thepreformed polyalkyleneimines are substituted. The compounds preparedfrom preformed polyalkyleneimines are usually more or less highlybranched. Their average molecular weight depends upon the degree ofpolymerization of the preformed polyethyleneimines orpolypropyleneimines, and can be from 500 to 500,000. In theirperformance, particularly in case of their use in washing, bleaching andcleansing agents, there is no essential difference between the linearand the branched copolymeric (N- alkylcarboxylic acid)-alkyleneimines.

The inner salts of the copolymers can be obtained from the aqueoussolutions by precipitation with mineral acids at the isoelectric pointor by treating with ion-exchange resins. The inner salts are amorphoussubstances in solid form, which are insoluble in organic solvents andalso predominantly in water, but are readily soluble in acids and bases.From the inner salts, the corresponding ammonium salts can be preparedby neutralization with ammonia or organic ammonium bases, such as mono-,dior triethanolamine, morpholine, or N-methylmorpholine. The washing,bleaching and cleansing agents according to the invention can alsocontain mixtures of different copolymcric (N-alkylcarboxylicacid)-alkyleneimines or their salts.

The agents according to the invention contain at least one othercleaning or bleaching component, such as non-ionic, anionic andamphoteric surface-active materials, inorganic or organic builders,oxygen-containing bleaching agents, as well as other conventionalwashing and cleansing ingredients. The copolymeric (N-alkylcarboxylicacid)-alkyleneimines or their salts, particularly the sodium salt, canbe added to these ingredients in the form of their solutions or in solidform after previous drying.

The washing and cleansing agents can also contain anionic basic washingcomponents of the sulfonate or sulfate type. Primarily alkylbenzenesulfonates, such as dodecyl-benzene sulfonate are suitable. However,olefin sulfonates, such as are obtained by sulfonation of primary andsecondary aliphatic monoolefins with gaseous sulfur trioxide andsubsequent alkaline or acidic hydrolysis, as well as alkylsulfonatesobtainable from n-alkanes by sulfochlorination or sulfoxidation andsubsequent hydrolysis, or neutralization, or by addition of bisulfite toolefins are also suitable. Also asulfo fatty acid esters, primary andsecondary alkyl sulfates and the sulfates of ethoxylated or propoxylatedhigher alcohols are suitable. Other compounds of this class which can beoccasionally present in the detergents are the higher molecular weightsulfated partial ethers and partial esters of polyhydric alcohols, suchas the alkali metal salts of the monoalkyl ethers, or monofatty acidesters of the glycerine monosulfuric acid esters, or of1,2-dihydroxy-propane-sulfonic acid. Also sulfates of ethoxylated orpropoxylated fatty acid amides and alkyl phenols as well as fatty acidtaurides and fatty acid isothionates are suitable.

Other appropriate anionic basic washing components are alkali metalsoaps of natural or synthetic fatty acids, such as sodium soaps ofcoconut, palm kernel or tallow fatty acids. As amphoteric basic washingcomponents, alkylbetaines and, particularly, alkylsulfobetaines aresuitable, for example, 3-(N,N-dimethyl-N-alkylammonium)-propane-l-sulfonate and 3-(N,N-dimethyl-N-alkylammonium )-2-hydroxypropanel -sulfonate, preferablywhere alkyl is a lower alkyl such as methyl or ethyl.

The anionic basic washing components can be present in the form of thealkali metal salts such as the sodium and potassium salts as well as theammonium salt, or as salts of organic bases, such as mono-, diandtriethanolamine. Where the named surface-active anionic and amphotericcompounds have a long-chain aliphatic hydrocarbon radical, the lattershould preferably be straightchained and should have from eight to 22carbon atoms. In the compounds with araliphatic hydrocarbon radicals thepreferred straight alkyl chains contain an average of from six to 16carbon atoms.

As non-ionic basic washing components are, in the first place, thepolyalkylene-glycolether derivatives of alcohols, fatty acids andalkylphenols which contain three to 30 ethyleneglycolether groups andeight to 20 carbon atoms in the hydrocarbon radical. Particularlysuitable are polyalkyleneglycolether derivatives in which the number ofoxyethylene groups is from five to and whose hydrocarbon radicals arederived from straight-chain primary alcohols with 12 to l8 carbon atoms,or from alkylphenols with a straight-chain alkyl chain of six to l4carbon atoms. By the addition of three to 15 mols of propylene oxide tothe last named polyethyleneglycolethers, or by converting them intoacetals, detergents are obtained which are distinguished by a speciallylow-foaming power.

Other suitable non-ionic basic washing components are the water-solublepolyethylene oxide adducts, adducted to polypropyleneglycol,ethylenediaminepolypropyleneglycol and alkylpolypropyleneglycol with oneto 10 carbon atoms in the alkyl chain. Preferably, these adducts containfrom 20 to 250 oxyethylene groups and 10 to oxypropylene groups in themolecule. The named compounds contain usually one to five oxyethyleneunits per oxypropylene unit. Also non-ionic compounds of the type ofaminooxides and sulfoxides which, if necessary, can also be ethoxylated,are usable.

As further mixture ingredients are neutral salts, such as sodium sulfateand sodium chloride, as well as compounds for adjustment of the pH, suchas bicarbonates, carbonates, borates and hydroxides of sodium andpotassium and acids, such as lactic and citric acid. The amount of thealkaline reacting compounds including alkali metal silicates andphosphates should be calculated so that the pH of a serviceable washingliquor for coarse laundry is nine to 12 and for fine laundry six tonine.

Appropriate mixture ingredients are also inorganic builders,particularly condensed phosphates, such as pyrophosphates,triphosphates, trimetaphosphates, tetrametaphosphates, as well as morehighly condensed phosphates in the form of the neutral or acidic alkalimetal salts such as the sodium and potassium salts as well as theammonium salt. Preferably alkali metal triphosphates and their mixturewith pyrophosphates are used. The condensed phosphates can also bepartly or completely substituted by organic complexing agents containingphosphorus or nitrogen atoms. Such compounds are the alkali metal orammonium salts of aminopolyphosphonic acids, particularlyamino-tri-(methylenephosphonic acid),ethylenediaminetetra-(methylenephosphonic acid),1-hydroxyethane-1,l-diphosphonic acid, methylenediphosphonic acid,ethylenediphosphonic acid as well as the higher homologs of the namedpolyphosphonic acids, as well as the alkali metal or ammonium salts oflow-molecular-weight amino-polycarboxylic acids, such as NTA and EDTA.As other builders, alkali metal silicates are suitable, particularlysodium silicate in which the ratio Na ozSio is 1:3.5 to

By appropriate combination of various surface-active basic washingcomponents or builders with each other, in many cases increasedeffectiveness, such as a higher cleaning property or lower foaming powercan be attained. Such improvements are possible, for example, bycombination together of anionic with non-ionic and/or amphotericcompounds, by combination of various non-ionic compounds with each otheror also by mixtures of basic washing components of the same type whichdiffer in regard to the number of carbon atoms or the number andposition of double bonds or branched chains in the hydrocarbon.Synergistically eftetraphosphates,

fective mixtures of inorganic and organic builders can also be used orcombined with the precedingly named mixtures.

Depending upon their respective use, the washing agents of the inventioncan contain oxygemreleasing bleaching compounds, such as hydrogenperoxide, alkali metal perborates, alkali metal percarbonates, alkalimetal perphosphates, urea hydrogen peroxide and alkali metal persulfatesor active chlorine compounds, such as alkali metal hypochlorites,chlorinated trisodium phosphate and chlorinated cyanuric acid, or itsalkali metal salts. The peroxide compounds can be present in a mixturewith bleaching activators and stabilizers, such as magnesium silicate.

Optical brighteners suitable for cellulosic fibers used in the washingagents of the invention are those of the diaminostilbene disulfonic acidtype of the formula:

in which X and Y have the following meanings: NI-I NI-I-CI-I NI-l-CI-I-CI-I OI-l, CH N-CI-I -CH OH, N(CH,-CH OH) morpholino,dimethylmorpholino, NI-I-C H NH-C H SO I-I, OCH Cl where X and Y can bethe same or not. Particularly suitable are those compounds in which X isan anilino and Y is a diethanolamino, or a morpholino group.

As optical brighteners also suitable for use in the washing agents ofthe invention are those of the diary!- pyrazoline type of the followingformula:

In this formula Ar and Ar are aryl radicals, such as phenyl,diphenyl, ornaphthyl which can have further substituents, such as hydroxy, alkoxy,hydroxyalkyl, amino, alkylamino, acylamino, carboxyl, sulfonic acid, andsulfonamide groups, or halogen atoms. Preferred is a1,3-diarylpyrazoline derivative in which the radical Ar is ap-sulfonamidophenyl group and the radical Ar is a p-chlorophenyl group.In addition to the brighteners, whiteners suitable for the brighteningof other fiber types can be present, for example, compounds of the typeof naphthotriazolestilbene sulfonates, ethylene-bis-benzimidazoles,ethylene-bisbenzoxazoles, thiophenebis-benzoxazoles,dialkylamino-coumarins, and the cyanoanthracenes. These brighteners ortheir mixtures can be present in the washing agents in amounts of from0.01 to 1.5 percent by weight, preferably from 0.1 to 1 percent byweight.

Further suitable mixture ingredients for the washing agents of theinvention are greying-inhibiting compounds, such as sodium celluloseglycolate, as well as the water-soluble alkali metal salts of syntheticpolymers which contain free carboxylic groups. These latter include thepolyesters or the polyamides of triand tetracarboxylic acids anddihydric alcohols or diamines, and also polymeric acrylic acid,methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconicacid, and aconitic acid as well as the mixed polymerizates of the namedunsaturated carboxylic acids, or their mixed polymerizates with olefins.

Washing agents intended for use in drum-washing machines containappropriately known foam-suppressing substances, such as saturated fattyacids with 20 to 24 carbon atoms, or their alkali metal soaps, ortriazine derivatives which can be obtained by reacting 1 mol cyanuricchloride with two to three mols of aliphatic, straight-chained,branched-chained or cyclic primary monoamines or by propoxylating, orbutoxylating melamine.

For a further improvement of the dirt-loosening properties of thewashing agents, according to the invention, they can also containenzymes from the class of proteases, lipases, or amylases. These enzymescan be of animal or plant origin, for example, those obtained fromdigestive ferments or yeasts, such as pepsin, pancreatin, trypsin,papain, catalase and diastase. Preferably used are enzymatic-activesubstances obtained from bacterial strains or molds, such as Bacillussubtilis and Streptomyces griseus which are relatively stable againstalkalis, peroxide compounds and anionic detergents and essentially notinactivated even at temperatures between 45 and C.

The washing and cleansing agents can be present in liquid, pasty orsolid form, as powder, granules or lumps. Liquid preparations maycontain water-miscible solvents, particularly lower alkanols such asethanol and isopropanol, as well as dissolving aids, such as the alkalimetal salts of benzene, toluene, xylene, or ethylbenzene sulfonic acids.For increasing the foaming power and for the improvement of the skincompatibility, alkylolamides such as fatty acid monoor diethanolamidesmay, if necessary, be added. The mixture can also contain dyes orodorizing substances, bactericidally active materials, activators aswell as fillers, for example, urea.

The preparation of the agents according to the invention can be done incustomary manner by mixing, granulating or spray-drying. Insofar asenzymes are used, it is recommended to mix them with the non-ionic basicwashing components and, if necessary, odorizing substances, or todisperse them in the melt of a salt containing water of crystallization,such as Glaubers salt, and to combine these premixtures with the otherpowdery ingredients. By this procedure, the enzymes are cemented withthe other powder particles so that the mixtures do not tend to dust orseparate.

The content of the washing, bleaching and cleansing agents of the saltsof the copolymeric (N-alkylcar-box ylic acid)-alkyleneimine amounts tofrom about 0.1 to 50 percent, preferably 0.2 to 25 percent by weight.The difference to percent is taken up by the previously named detergentand bleaching active substances as well as, if necessary, the additionalbuilders to improve the cleaning power. The qualitative and quantitativecomposition of these additional ingredients depend widely upon thespecial use of these agents. It corresponds in the case of thetechnically particular important washing and cleansing agents to thefollowing recipe (data in percent by weight):

1 to 40 percent of at least one compound from the class of the anionic,non-ionic and amphoteric detergents;

to 80 percent, preferably,

10 to 80 percent of at least one non-surface-active cleaning,intensifying or complexing builder;

0 to 50 percent, preferably 10 to 50 percent, ofa percompound,especially sodium perborate, with or without water of crystallization,as well as their mixtures with stabilizers and activators;

0 to 60 percent, preferably 0.1 to 20 percent, of

other auxiliary and supplementary substances.

The detergent substances can consist of up to 100 percent, preferablyfrom to 70 percent, of compounds of the sulfonate and/or the sulfatetype, up to 100 percent, preferably from 5 to 40 percent, of compoundsof the non-ionic polyglycolether type, and up to 100 percent, preferablyfrom to 50 percent, of soaps. The builders can consist of up to 100percent, preferably from 25 to 95 percent, of alkali metal triphosphatesand their mixtures with alkali metal pyrophosphates, up to 100 percent,preferably from 5 to 50 percent, of an alkali salt of a complexing agentfrom the class of polyphosphonic acids, nitrilotriacetic acid,ethylenediaminetetraacetic acid, and up to 100percent, preferably from 5to 75 percent, of at least one compound of the class of alkali metalsilicates, alkali metal carbonates and alkali metal borates.

To the additional auxiliary and supplementary substances belong, inaddition to the optical brighteners, especially the foam inhibitorswhich can be present in the agents according to the invention in anamount of up to 5 percent, preferably from 0.2 to 3 percent; also theenzymes which can be present in an amount up to 5 percent, preferablyfrom 0.2 to 3 percent; and the graying inhibitors which can be presentin an amount up to 5 percent, preferably from 0.2 to 3 percent.

The copolymeric (N-alkylcarboxylic acid)-alkyleneimines and their saltsimpart to the washing, cleansing and bleaching agents, according to theinvention, a high washing and cleansing power, as well as improveddirt-carrying power. They are effective stabilizers for peroxidecompounds and are less attacked by peroxide compounds than knowncomplexing agents. They are, therefore, suitable for the stabilizationof 'liquid bleaching detergents, such as those containing hydrogenperoxide and compounded liquid bleaching agents.

The preparation of such agents has failed so far because of the lowstorage stability of the peroxide compounds. The new compounds protect,in addition, the oxygen-sensitive ingredients of washing agents,particularly the optical brighteners and enzymes effectively againstoxidative destruction. in contrast to many known oxidation inhibitors,they do not diminish the bleaching power of the agents. The agents canbe easily degraded biologically and have the advantage that they canreplace completely or partially the polymeric phosphates which havepreviously necessarily been present in washing agents, so that becauseof a lesser amount of phosphate ions in the sewage, they do not promotethe growth of algae in rivers and lakes.

The following examples are illustrative of the practice of the inventionwithout being limitative. in the following, some recipes are given whichhave proven particularly good in practice.

EXAMPLES A. Powdery, Low-Foaming Washing Agent 3 to 15 percent of asulfonate basic washing component from the class of alkylbenzenesulfonates, olefin sulfonates and n-alkane sulfonates (sodium salts),

0.5 to 5 percent of an alkylpolyglycolether (alkyl C to C oralkylphenolpolyglycolether (alkyl C to C with five to 10 oxyethylenegroups,

0 to 5 percent of a C to C soap (sodium salt),

0.2 to 5 percent of foam inhibitors from the class of trialkylmelaminesand saturated fatty acids with 20 to 24 carbon atoms, or their alkalimetal soaps,

10 to 50 percent of a condensed alkali metal phosphate from the class ofthe pyrophosphates or the tripolyphosphates,

0.1 to 25 percent of the copolymeric (N-alkylcarboxylicacid)-alkyleneimines or their alkali metal salt,

1 to 5 percent of sodium silicate,

l0 to 35 percent of sodium perborate tetrahydrate,

0 to 5 percent of enzymes,

0.05 to 1 percent of at least one optical brightener from the class ofdiaminostilbene disulfonic acid or diarylpyrazoline derivatives,

0.1 to 30 percent of an inorganic alkali metal salt from the class ofthe carbonates, bicarbonates, borates, sulfates and chlorides,

0 to 4 percent of magnesium silicate,

. 0.5 to 3 percent of sodium celluloseglycolate. B. Powdery Foaming FineWashing Agent 1 to 30 percent of a sulfonate basic washing component(sodium salt), v

0.5 to 10 percent of alkylpolyglycolether sulfate (alkyl C to C one tofive oxyethylene groups),

0 to 20 percent of an alkylpolyglycolether (alkyl C to C oralkylphenolpolyglycolether (alkyl C to C with five to 12 oxyethylenegroups,

0.2 to 25 percent of the copolymeric (N-alkylcarboxylicacid)-alkyleneimines or their alkali metal salt,

0 to 5 percent of a higher fatty acid ethanolamide or diethanolamide,

0 to 20 percent of sodium tripolyphosphate,

0 to 1 percent of a brightener from the class of the diarylpyrazolinederivatives and its mixtures with polyester brighteners,

3 to percent of sodium sulfate.

C. Liquid Washing Agent 0.5 to 10 percent of a sulfonate basic washingcomponent (potassium salt),

0 to 10 percent of alkylpolyglycolether sulfate (alkyl C to C l to 5oxyethylene groups),

0.2 to 25 percent of the copolymeric (N-alkylcarboxylicacid)-alkyleneimines or their alkali metal salts,

0.1 to 5 percent of fatty acid amide-glycolether condensate (alkyl C toC l to 10 oxyethylene I groups),

1 to 10 percent of solution aids from the class of the alkali metalsalts of benzene, toluene, or xylene sulfonic acids,

to 30 percent of neutral or acid potassium pyrophosphate,

0 to 10 percent of organic solvent media from the class of the C to Calcohols and ether alcohols,

0 to 1 percent of optical brighteners from the class of of thediaminostilbene disulfonic acids and diarylpyrazoline derivatives,

0 to percent of hydrogen peroxide,

Residue: Water, perfumes, dyes, preservatives.

D. Steeping and Pre-Washing Agent 0.5 to 5 percent of sulfonate basicwashing component (sodium salt),

0 to 3 percent of compounds from the class of alkylpolyglycolethers(alkyl C to C and alkylphenolpolyglycolethers (alkyl C to C with five to12 oxyethylene groups,

0.1 to percent of the copolymeric (N-alkylcarboxylicacid)-alkyleneimines or their alkali metal salts,

10 to 50 percent of sodium carbonate,

1 to 5 percent of water glass,

0 to 5 percent of magnesium silicate,

0 t0 5 percent of enzymes.

E. Dishwashing-Machine Washing Agents 0.1 to 3 percent of compounds fromthe class of the alkylpolyglycolether (alkyl C to C18),alkylphenolpolyglycolether (alkyl C to C with five to 30 oxyethylenegroups and five to 30 oxypropylene groups, and ethoxylatedpolypropyleneglycols,

0.2 to 25 percent of the copolymeric (N-alkylcarboxylicacid)-alkyleneimines or their alkali metal salts,

45 to 95 percent of pentasodium triphosphate,

1 to 40 percent of sodium silicate (Na,O:SiO 1:1

0 to 5 percent of potossium dichloroisocyanurate,

0 to 2 percent of foaming inhibitors.

F. Liquid Rinsing and Cleansing Agent:

5 to 30 percent of a sulfonate basic washing component (potassium salt),

2 to percent of alkylpolyglycolether sulfate (alkyl C,, to C one to fiveoxyethylene groups),

0.2 to 10 percent of alkali metal salts of the copolymeric(N-alkylcarboxylic acid)-alkyleneimines,

0 to percent of organic solvents from the class of C to C alcohols andether alcohols,

l to 10 percent of solution aids such as sodium toluene sulfonate,sodium xylene sulfonate and urea,

Residue: Water, perfumes, dyes, preservatives.

G. Bleaching Agents:

0.2 to percent of the copolymeric (N-alkylcarboxylic acid)-alkyleneimines or their alkali metal salts,

10 to 95 percent of per-compounds,

0 to 50 percent of alkaline reacting compounds from the class of alkalimetal hydroxides, carbonates, silicates and phosphates,

0 to 50 percent of bleaching activators,

0 to 5 percent of anionic and/or non-ionic detergents,

0 to 10 percent of other ingredients, such as corrosion inhibitors,optical brighteners, neutral salts, magnesium silicate.

H. Alkaline Cleansers:

0.1 to 25 percent of the copolymer (N-alkylcarboxylicacid)-alkyleneimines or their alkali metal salts, 0.5 to 50 percent ofsodium silicate (Na O:SiO 1:1

0.5 to percent of sodium hydroxide,

0 to 40 percent of trisodium phosphate,

0 to 40 percent of condensed alkali phosphates,

0 to 40 percent of sodium carbonate,

0 to 10 percent of hydroxyethane diphosphonate (sodium salts),

0 to 5 percent of anionic and/or non-ionic detergents.

l. Scouring Agent:

1 to 10 percent of anionic and/or non-ionic basic washing components,

0.1 to 5 percent of alkali metal salts of the copolymeric(N-alkylcarboxylic acid)-alkyleneimines,

80 to 95 percent of abrasive agents,

0 to 10 percent or cleansing salts of the class of alkali metalpolyphosphates, alkali metal silicates, alkali metal borates, and alkalimetal carbonates,

0 to 10 percent of alkali metal dichloroisocyanurate.

metal PREPARATION OF THE MONOMERIC STARTING MATERIALS AND OF THE MIXEDPOLYMERS For the preparation of the monomeric N-succinicester-ethyleneimine, dibutyl maleate and aziridine in a mol ratio of 1:2were heated for 24 hours at 30 to 40 C in the presence of 1 mol percentof sodium methylate. The N-(dibutylsuccinate)-aziridine was thenisolated from the reaction mixture by fractionate distillation (boilingpoint 122 C at 0.4 mm Hg). For the preparation of monomericN-tricarballylic acid esterethyleneimine, dibutyl aconitate andaziridine in a mol ratio of 1:1 were heated for 24 hours at 30 to 40 Cin the presence of 1 mol percent of sodium methylate. The productobtained was used without intermediary purification. In an analogousmanner aziridine was heated with methyl acrylate, dimethyl itaconate, oramethyleneglutaric ester in a mol ratio of 1:1, in the presence of 1 molpercent of sodium methylate and thereby the propionic acid ester,methylenesuccinic acid ester, and methyleneglutaric acid esterderivatives were obtained. The N-(methyl acetate)-ethyleneimine wasobtained by condensation of methyl chloroacetate with aziridine in thepresence of aqueous alkali.

The monomeric ethyleneimine derivatives were mixed according to the molratios listed in the following examples and polymerized by the stepwiseaddition of l to 5 mol percent diethyl sulfate in an inert gasatmosphere within 5 to 48 hours at a temperature not higher than 50 C.For the saponification the copolymers, dissolved in methanol, weretreated with the equivalent amount of 20 percent aqueous sodiumhydroxide solution. The solution was heated to 80 to C and the methanolwas removed by distillation. After heating for 5 to 10 hours, withfrequent addition of water, the saponification was completed and thesodium salts of the linear copolymers were then iso- 5 lated by spraydrying.

1,800, 15,000 and 40,000 wereheated for 24 hours at 80 to 90 C in a 20percent aqueous solution with 50 percent of the stoichiometric amount,required for a 100 percent N-alkylation, of maleic acid. The pH wasadjusted to 10 to 11 by addition of sodium hydroxide during thereaction. Subsequently, the reaction was completed on addition of 55 molpercent of sodium chloroacetate by heating for hours at 80 to 90 C withaddition of sodium hydroxide to maintain a pH of to 11. The solution wasfreed of salts by the use of anionic and cationic exchange resins. Thecopolymers were converted to the sodium salts by neutralization withsodium hydroxide.

EXAMPLES 1 TO 13 The cleaning action of washing agents that containedone part by weight of an anionic basic washing component(Na-n-dodecylbenzene sulfonate) and two parts by weight of one of thelinear copolymeric N-alkylcarboxylic acid-ethyleneimines in the form ofits sodium salt, as listed in Table II, were compared. With thesewashing agents, cotton cloth which had been soiled with a synthetic soilcontaining soot, iron oxide and cutaneous fat was washed in a laboratorywashing machine where the washing liquor was heated from 20 to 90 Cwithin minutes and kept at 90 C for another 15 minutes. The washingagent concentration was 3 gm/l. The water hardness was 16 dH. The weightratio of textile to liquor was 1:12. Subsequently, the washed cloth wasrinsed with water four times, centrifuged and dried. The percent ofwhiteness was determined with a photometer (soiled cloth 0 percent,original cloth 100 percent) and is shown in the following Table 11 aswell as the composition of the washing agents.

The results of the washing tests of Table 11 show that the copolymeric(N-alkylcarboxylic acid)- ethyleneimines are superior to the other knownbuilders, among them sodium ethylenediaminetetraacetate.

TABLE 11 Amount of the Carboxylic Acids in the Linear MolecularBrighten- Example Copolymer (Na-salt) Weight ing 1 50% succinic acid 85078.6 2 50% acetic acid 1280 78.6 3 75%succinic acid 950 79.0 4 25%aceticacid 1420 79.2 5 50% succinic acid 50%methy1enesuccinic 1680 79.1 acid 650% succinic acid 50% methyleneglutaric 2400 79.4 acid 7 50%tricarballylic acid 650 78.4 8 50% acetic acid 1760 78.8 9 90%tn'carballylic acid 1450 80.3

10% acetic acid 10 60% tricarballylic acid 3400 78.2

40% propionic acid 1 1 50% tricarballylic acid 1380 79.8 12 50% succinicacid 2300 80.1 13 80% tricarballylic acid 980 80.5

succinic acid Na-ethylenediaminotetraacetate 75.4

EXAMPLES 14 TO 20 A washing agent of the following composition was used(data in percent by weight):

Percent 8.0 Na-n-dodecylbenzene sulfonate v 5.0 Sodium soap of C to Cfatty acids 3.0 Oleyl alcohol polyethyleneglycolether (10 oxyethylenegroups) 40.0 Pentasodium triphosphate 5.0 Sodium silicate (Na O-3-3$10,)

2.0 Magnesium silicate 1.0 Sodium cellulose glycolate 25.0 Sodiumperborate-tetrahydrate 8.0 Water 0.8 Brightener of the pyrazoline type0.2 Brightener of the diaminostilbene type The brighteners had thefollowing structures:

O2NH2 Pyrazollne type HN Y Diaminostilbena type With these agents,textiles of polyamide fiber (Perlon registered trademark) were washed ina laboratory washing machine where the washing. liquor was heated from20 to 60 C within 15 minutes and was kept at this temperature for anadditional 15 minutes. The washing agent concentration was 5 gm/l andthe weight ratio of textiles to liquor was 1:30. The water used had ahardness of 16 dl-l as well as a copper ion content of 10" mols perliter. The degree of whiteness of the four times rinsed and then driedwash was determined by photometer. The results are summarized in Table111. These results demonstrate the superiority of the use of thepolymers of the present invention.

The branched copolymers used in Examples 19 and 20 were obtained byreaction of preformed polyethyleneimine with maleic acid andchloroacetic acid in aqueous sodium hydroxide.

TABLE III Degree of amount of the carboxylic whiteness acids in thecopolymer molecular after Ex. (Na-salt) weight 1 wash 5 washes 14 50%succinic acid 1,280 108 1 15 50% acetic acid 15 75% succinic acid 1,420109 1 15 25% acetic acid 16 50% succinic acid 1,680 108 114 50%methylenesuccinic acid 17 50% tricarballylic acid 1,760 108 116 50%acetic acid 18 50% tricarballylic acid 1,380 l 1 17 succinic acid 19 40%branched succinic acid 6,400 107 1 50% acetic acid 10% unsubstituted 2040% branched succinic acid 120,000 108 1 16 57% acetic acid 3%unsubstituted Na-Nitrilotriacetate 100 104 Na-ethylenediaminotetra- 1031 l0 acetate EXAMPLES 21 TO 24 Textile samples of grey cotton clothsoiled with tea were washed by applying the washing agent used inExamples 14 to 20, with the addition of 2 percent by weight ofcopolymeric, linear N-alkylcarboxylic acidethyleneimines for 30 minutesat 90 C. The concentration of the washing agent was 5 gm/l. The weightratio of textile to washing liquid was 1:10 and the hardness of the tapwater was 16 dH. The reflection values, determined by photometer, of thethree-times rinsed and dried textile samples are summarized in thefollowing Table IV.

EXAMPLES 25 AND 26 An aqueous solution containing 0.62 gm/l of sodiumperborate was prepared from a bleaching agent consisting of 154 gm (1mol) of sodium perborate and 1 mol of a copolymeric N-alkylcarboxylicacid-ethleneimine (159 gm in Example 25 and 188 gm in Example 26) andadjusted to a pH of 10 by addition of dilute sodium hydroxide solution.Another bleaching solution, also adjusted to a pH of 10 'with sodiumhydroxide, contained per liter 5 millimol (0.136 gm) of hydrogenperoxide and 4 millimol (0.63 gm in Example 25 and 0.8 gm in Example 26)of the complexing agent. The decrease in the active-oxygen content ofthese solutions at 100 C was determined every 30 minutes by iodometrictitration. For comparison the determination was repeated with equimolaramounts of known perborate stabilizers (EDTA ethylenediaminetetraaceticacid, NTA nitrilotriacetic acid). The results are summarized in thefollowing Table V. They show the particular stability of the agents,according to the invention to oxidizing agents.

The preceding specific embodiments are illustrative of the practice ofthe invention. It is to be understood, however, that other expedientsknown to those skilled in the art may be employed without departing fromthe spirit of the invention or the scope of the appended claims.

We claim:

1. A washing, bleaching and cleansing agent having a content of from 50to 99.9 percent, by weight, of customary components of washing,bleaching and cleansing agents and from 0.1 to 50 percent, by weight ofa polyalkyleneimine selected from the group consisting of (l copolymericN-alkylcarboxylic acid-alkyleneimine having an average molecular weightof from 500 to 500,000 and recurring N-alkylcarboxylicacid-alkyleneimine units of different structure of the formulas 1 and IIwherein R represents a member selected from the group consisting of Hand CH R represents a member selected from the group consisting of H andCH X represents a member selected from the group consisting of H and CHCOOH, Y represents a member selected from the group consisting of H, CH-COOH and CH -CH -COOH and n represents an integer of from one to two,with the proviso that when X is H, Y is H or --CH,-CH,-COOH, the ratioof recurring N-alkylcarboxylic acid-alkyleneimine units of formula 1 tothose of formula 11 being from one to to 100 to one and (2) their alkalimetal, ammonium and organic ammonium salts with bases selected from thegroup consisting of mono-, diand triethanolamine, morpholine andN-methyl morpholine, said customary components of washing, bleaching andcleansing agents consisting essentially of from to 40 percent by weightof at least one compound selected from the group consisting of anionic,non-ionic and amphoteric surface-active basic washing components, from 0to 80 percent by weight of at least one builder selected from the groupconsisting of condensed inorganic phosphate builders, alkali metalsilicates, carbonates, bicarbonates, borates, sulfates and chlorides,alkali metal and ammonium salts of aminopolyphosphonic acids andlow-molecularweight aminopolycarboxylic acids, from 0 to 100 percent byweight of a bleaching compound selected from the group consisting ofhydrogen peroxide, urea hydrogen peroxide, alkali metal perborates,percarbonates, perphosphates', persulfates, hypochlorites, chlorinatedtrisodium phosphate and chlorinated cyanuric acid and its alkali metalsalts, and mixtures thereof with magnesium silicates, and from 0 to 60percent of other auxiliary and supplementary components of washingagents selected from the group consisting of optical brighteners,greying-inhibitors, foam-suppresacid-alkyleneimine contains less than 50percent of unsubstituted recurring alkyleneimine units.

5. The washing, bleaching and cleansing agent of claim 4 wherein saidcopolymeric N-alkylcarboxylic acid-alkyleneimine contains less than 30percent of unsubstituted recurring alkyleneimine units.

6. The washing, bleaching and cleansing agent of claim 1 wherein R and Rare hydrogen.

2. The washing, bleaching and cleansing agent of claim 1 wherein saidratio of recurring N-alkylcarboxylic acid-alkyleneimine units of formulaI to those of formula II is from one to 10 to 10 to one.
 3. The washing,bleaching and cleansing agent of claim 1 wherein said polyalkyleneiminesare present in an amount of from 0.5 to 25 percent by weight.
 4. Thewashing, bleaching and cleansing agent of claim 1 wherein saidcopolymeric N-alkylcarboxylic acid-alkyleneimine contains less than 50percent of unsubstituted recurring alkyleneimine units.
 5. The washing,bleaching and cleansing agent of claim 4 wherein said copolymericN-alkylcarboxylic acid-alkyleneimine contains less than 30 percent ofunsubstituted recurring alkyleneimine units.
 6. The washing, bleachingand cleansing agent of claim 1 wherein R and R'' are hydrogen.